CN104091915B - The electrochemistry storage sodium combination electrode of a kind of high power capacity and stable circulation and preparation method - Google Patents
The electrochemistry storage sodium combination electrode of a kind of high power capacity and stable circulation and preparation method Download PDFInfo
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Abstract
The invention discloses the electrochemistry of a kind of high power capacity and stable circulation storage sodium combination electrode and preparation method, its electrochemistry storage sodium active substance is MoS2-nanometer watt/composite nano materials of Graphene, MoS in composite nano materials2Nanometer watt and the ratio of amount of substance of Graphene be 1:1-1:13, MoS2Nanometer watt for the layer structure of few number of plies, the average number of plies about 4 layers, the component of combination electrode and mass percentage content thereof be: MoS2Nanometer watt/graphene composite nano material is 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.Preparation process: first obtain MoS2Nanometer watt/graphene composite nano material, then with acetylene black and Kynoar furnishing pastel, this pastel is coated onto on the Copper Foil of collector, after vacuum drying rolling obtain.The MoS of the present invention2Nanometer watt/Graphene electrochemistry storage sodium combination electrode there is high reversible storage sodium capacity, application prospect is extensive.
Description
Technical field
The present invention relates to electrochemistry storage sodium electrode and preparation method thereof, particularly relate to and use MoS2Nanometer watt/electrochemistry storage sodium combination electrode of a kind of high power capacity prepared by Graphene and stable circulation and preparation method thereof, belong to inorganic composite nano material, new energy materials preparation field.
Background technology
Along with the development of modern mobile communication, new-energy automobile and intelligent grid, novel electrochmical power source serves more and more important effect in modern society.Traditional secondary cell, if lead-acid accumulator is owing to it is containing harmful metallic element Pb, its application is restricted.Lithium ion battery has the excellent properties such as high specific energy, memory-less effect, environmental friendliness, is widely used in the Portable movable electrical equipment such as mobile phone and notebook computer.As electrokinetic cell, lithium ion battery is also with a wide range of applications in electric bicycle, electric automobile and intelligent grid etc..But limited due to the safety never solution carefully of lithium ion battery and lithium resource, lithium ion battery still there is also a lot of work as the extensive use of electrokinetic cell and storage battery and to do.Along with the development of new-energy automobile and the large-scale application of storage battery are in the urgent need to finding the secondary cell of a kind of a kind of cheap, environmental friendliness that can substitute existing secondary cell system and height ratio capacity.Owing to sodium ion has less radius, it is possible to electrochemical intercalation and deintercalation are in the compound of some Rotating fields, such as inorganic transition metal oxide, sulfide etc..Additionally sodium also have aboundresources, cheap, nontoxic and process the advantages such as convenient.Therefore, chargeable sodium-ion battery also becomes the research system of a new secondary cell in recent years.But up to the present store the electrode material of sodium or little as high performance electrochemistry.
MoS2Have with graphite-like like layer structure, be the S-Mo-S that combines of very strong covalent bond in its layer, be then more weak Van der Waals force between layers.MoS2More weak interlaminar action power and bigger interlamellar spacing allow by insertion reaction at its interlayer external atom of introducing or molecule.Such characteristic makes MoS2Material can as the material of main part of insertion reaction.Therefore, MoS2It it is the electrode material of a kind of electrochemistry storage sodium having development and application prospect.But general MoS2Nano material electrochemistry storage sodium poor-performing, its electrochemistry storage sodium capacity relatively low (only 50-100mAh/g), have impact on its practical application.
Two-dimension nano materials has the characteristic of numerous excellence with the pattern of its uniqueness, and its research causes the great interest of people.Graphene is most typical two-dimension nano materials, and the two-dimensional nano chip architecture of its uniqueness makes the performances such as the physics of its numerous uniquenesses, chemistry and mechanics, has important scientific research meaning and technology application prospect widely.Graphene has high specific surface area, high conduction and heat conductivility, high charge mobility, excellent mechanical property, the characteristic of these excellences makes Graphene be with a wide range of applications in fields such as nano electron device, novel catalyst material and electrochemistry energy storage and energy conversion.
The immense success that the discovery of Graphene and research thereof obtain excites the great interest that other inorganic two-dimension nano materials are studied by people, such as the transition metal dichalcogenide etc. of monolayer or few number of plies.Recently, Graphene concept has expanded to the inorganic compound of other layer structures from material with carbon element, namely for the inorganic material of layer structure, when its number of plies reduces (less than 8 layers), when especially reducing to monolayer, its electronic property or band structure can produce obvious change, thus causing which show the physics different from corresponding body phase material and chemical characteristic.Except Graphene, as body phase MoS2Reduce to few number of plies (especially during monolayer), it is shown that Wuli-Shili-Renli system approach visibly different with body phase material.Research shows monolayer or the MoS of few number of plies2Nanometer sheet has better electrochemistry storage sodium performance.But the electrode material of sodium, MoS is store as electrochemistry2Electric conductivity low between layers have impact on the performance of its application.
Due to MoS2Nanometer sheet has similar two-dimensional nano sheet pattern with Graphene, and both have good similarity on microscopic appearance and crystal structure.If by MoS2Nanometer sheet and Graphene compound prepare both composites, the high conduction performance of graphene nanometer sheet can improve the electric conductivity of composite further, strengthen the electron transmission in electrochemistry storage sodium electrode process, it is possible to improve the electrochemistry storage sodium performance of composite further.With common MoS2Nanometer sheet compares, the MoS of little nanometer tiles pattern2Not only there is more edge, it is provided that more short sodium ion diffusion admittance, and load is on Graphene, has more contact area with electrolyte.Therefore MoS2Nanometer watt/composite nano materials of Graphene can show the electrochemistry storage sodium performance being obviously enhanced.
But, up to the present, use MoS2Nanometer watt/graphene composite nano material stores sodium combination electrode and preparation thereof as the electrochemistry of electroactive substance and have not been reported.First the present invention is raw material with graphene oxide and sodium molybdate, the hydrothermal method assisted by Gemini surface active agent and heat treatment subsequently, is prepared for MoS2Nanometer watt/composite nano materials of Graphene, then use MoS2Nanometer watt/composite nano materials of Graphene stores the active substance of sodium as electrochemistry, is prepared for the combination electrode of electrochemistry storage sodium.The present invention prepares MoS2Nanometer watt/method of graphene composite nano material electrochemistry storage sodium combination electrode has simple, convenient and is easily enlarged industrial applications a little.
Summary of the invention
It is an object of the invention to provide the electrochemistry of a kind of high power capacity and stable circulation storage sodium combination electrode and preparation method thereof, the electrochemistry storage sodium active substance of combination electrode is MoS2-nanometer watt/composite nano materials of Graphene, MoS in composite nano materials2Nanometer watt and the ratio of amount of substance of Graphene be 1:1-1:3, MoS2Nanometer watt for the layer structure of few number of plies, the component of combination electrode and mass percentage content thereof be: MoS2Nanometer watt/graphene composite nano material 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
In technique scheme, the layer structure of few number of plies refers to the number of plies layer structure 6 layers or less than 6 layers, described MoS2Nanometer watt the average number of plies be 4 layers.
The preparation method of the electrochemistry storage sodium combination electrode of above-mentioned high power capacity and stable circulation comprises the following steps:
(1) by graphene oxide ultrasonic disperse in deionized water, add the double; two ammonium bromide (see accompanying drawing 1) of Gemini surface active agent N-dodecyl trimethylene diamine, and be sufficiently stirred for, then Cys and sodium molybdate it are sequentially added into, and be stirred continuously and make Cys and sodium molybdate be completely dissolved, the ratio of the amount of substance of Cys and sodium molybdate consumption is 5:1, and the ratio of sodium molybdate and the amount of substance of graphene oxide is at 1:1-1:3；
(2) mixed dispersion that step (1) obtains is transferred in hydrothermal reaction kettle, and add deionized water and adjust volume to the 80% of hydrothermal reaction kettle nominal volume, the concentration of the double, two ammonium bromide of Gemini surface active agent N-dodecyl trimethylene diamine is 0.01 ~ 0.02mol/L, the content of graphene oxide is 30-65mmol/L, this reactor is put in constant temperature oven, at 230-250 DEG C after hydro-thermal reaction 24h, it is allowed to naturally cool to room temperature, hydro-thermal reaction solid product is collected with centrifugation, and fully wash with deionized water, vacuum drying at 100 DEG C, by the hydro-thermal reaction solid product that obtains in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mixing gas, hydrogen volume mark is 10%, finally prepare MoS2Nanometer watt/composite nano materials of Graphene；
(3) by the MoS of above-mentioned preparation2Nanometer watt/graphene composite nano material as electrode electrochemistry store sodium active substance, under agitation being sufficiently mixed the uniform pastel of furnishing with the N-Methyl pyrrolidone solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%, each constituent mass percentage ratio is: MoS2Nanometer watt/graphene composite nano material 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuum drying at 110 DEG C, rolling obtain MoS2Nanometer watt/Graphene electrochemistry storage sodium combination electrode.
Above-mentioned graphene oxide adopts the Hummers method improved to prepare.
The hydrothermal method with the double; two ammonium bromide assistance of Gemini surface active agent N-dodecyl trimethylene diamine of the present invention prepares MoS2Nanometer watt/method of graphene composite nano material have the advantage that surface of graphene oxide and edge with a lot of oxygen-containing functional groups (such as hydroxyl, carbonyl, carboxyl), these oxygen-containing functional groups make graphene oxide more easily be dispersed in water or organic liquid, but these oxygen-containing functional groups make surface of graphene oxide with negative charge so that graphene oxide and the MoO with negative charge4 2-Ion is incompatible, and double; two for Gemini surface active agent N-dodecyl trimethylene diamine ammonium bromide are first adsorbed onto surface of graphene oxide by electrostatic interaction by the present invention so that it is with part positive charge, due to electrostatic interaction, MoO4 2-Ion is just easy to interact with the graphene oxide having adsorbed Gemini surface active agent combine.The more important thing is, compared with common single cationic surfactant, the double; two ammonium bromide of Gemini surface active agent N-dodecyl trimethylene diamine there are 2 positively charged quaternary ammonium hydrophilic groups, there is enough hydrophilic, and there is between electronegative graphene oxide higher mutual electrostatic interaction；The double; two ammonium bromide of N-dodecyl trimethylene diamine also has 2 hydrophobic long alkyl chain groups (see accompanying drawing 1), and hydrophobicity is higher.The double; two ammonium bromide of N-dodecyl trimethylene diamine is adsorbed on graphenic surface, and its hydrophobic group exists (see accompanying drawing 2) with irregular " brush head " form of bending, and this version result in water-heat process and the heat treatment back loading MoS at graphenic surface2The pattern having nanometer watt.This undersized MoS2Nanometer watt there is more edge, store sodium material as electrochemistry, it is provided that more short sodium ion diffusion admittance, contribute to strengthening its electrochemistry storage sodium performance；It addition, MoS2Nanometer watt/graphene composite material can increase the contact area of itself and electrolyte, it is possible to further help in and improve its chemical property.Therefore present invention MoS2Nanometer watt/the electrochemistry storage sodium combination electrode prepared as electroactive substance of graphene composite material has a high electrochemistry storage sodium capacity, excellent cycle performance and be obviously enhanced large current density electrical characteristics.
Accompanying drawing explanation
The double; two ammonium bromide structural representation of Fig. 1 Gemini surface active agent N-dodecyl trimethylene diamine.
Fig. 2 Gemini surface active agent is adsorbed on the schematic diagram of surface of graphene oxide.
The MoS that Fig. 3 embodiment 1 prepares2Nanometer watt/XRD figure of graphene composite nano material.
The MoS that Fig. 4 embodiment 1 prepares2Nanometer watt/the SEM shape appearance figure of graphene composite nano material and transmission electron microscope photo.
MoS prepared by the comparative example of Fig. 5 embodiment 12TEM and the HRTEM photo of nanometer sheet and graphene composite nano material.
Detailed description of the invention
The present invention is further illustrated below in conjunction with embodiment.
Graphene oxide in following example adopts the Hummers method improved to prepare: 0oUnder C ice bath, by 10.0mmol (0.12g) graphite powder dispersed with stirring to 50mL concentrated sulphuric acid, it is stirred continuously down and is slowly added into KMnO4, added KMnO4Quality be 4 times of graphite powder, stir 50 minutes, when temperature rises to 35 DEG C, be slowly added into 50mL deionized water, be stirred for 30 minutes, add the H of 15mL mass fraction 30%2O2, stir 30 minutes, through centrifugation, obtain graphene oxide with after the HCl solution of mass fraction 5%, deionized water and acetone cyclic washing successively.
Embodiment 1
1) by 2.5mmol graphene oxide ultrasonic disperse in 60mL deionized water, add the double; two ammonium bromide of 0.8mmol Gemini surface active agent N-dodecyl trimethylene diamine, and be sufficiently stirred for, then it is sequentially added into 0.76g (6.25mmol) Cys and 0.3g (1.25mmol) sodium molybdate (Na2MoO4·2H2O), and it is stirred continuously and makes Cys and sodium molybdate be completely dissolved, adjust volume to about 80mL with deionized water；
2) obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24h, allow it naturally cool to room temperature, collect solid product with centrifugation, and fully wash with deionized water, vacuum drying at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mixing gas, the volume fraction of hydrogen is 10%, prepares MoS2Nanometer watt/composite nano materials of Graphene, MoS in composite nano materials2It is 1:2 with the ratio of Graphene amount of substance.MoS is obtained to prepared with XRD, SEM and TEM2Nanometer watt/composite nano materials of Graphene characterizes, XRD analysis result (see accompanying drawing 3) shows MoS in composite nano materials2For the layer structure of few number of plies, the average number of plies is 4 layers.SEM pattern and TEM photo (see accompanying drawing 4) also show load MoS on Graphene2Having little nanometer shoe looks, between 2 and 6, most numbers of plies are 4 layers to its number of plies, consistent with XRD analysis；
3) by the MoS of above-mentioned preparation2Nanometer watt/graphene composite nano material as electrochemistry store sodium electrode active material, with acetylene black, the N-Methyl pyrrolidone solution of the Kynoar of carboxymethyl cellulose and mass fraction 5% is under agitation sufficiently mixed the uniform pastel of furnishing, this pastel is coated onto equably on the Copper Foil of collector, vacuum drying at 110 DEG C, then rolling obtain MoS2Nanometer watt/Graphene electrochemistry storage sodium combination electrode, in combination electrode, each constituent mass percentage ratio is: MoS2Nanometer watt/graphene composite nano material 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%.
Electrochemistry storage sodium performance test: with combination electrode for working electrode, with metallic sodium sheet as to electrode, electrolyte is 1.0mol/LNaClO4Perfluorocarbon acid vinyl acetate/Allyl carbonate (FEC/PC, 1:1, volume ratio) solution be electrolyte, porous polypropylene film (Celguard-2400) is barrier film, is assembled into test battery in the suitcase of full argon.Storing sodium performance by the electrochemistry of constant current charge-discharge test compound electrode, charge and discharge cycles carries out on programme controlled auto charge and discharge instrument, charging and discharging currents density 50mA/g, voltage range 0.01 ~ 3.0V.Test result shows: MoS2Nanometer watt/electrochemistry of the graphene combination electrode storage initial reversible capacity of sodium is 435mAh/g, after 50 circulations, reversible capacity is 425mAh/g, it is shown that high specific capacity and excellent stable circulation performance；When high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 372mAh/g, it is shown that the high power charging-discharging characteristic (comparing with following comparative example) that it is obviously enhanced.
Comparative example
Adopt Dodecyl trimethyl ammonium chloride cationic surfactant, be prepared for MoS by above-mentioned similar approach2Nanometer sheet/Graphene electrochemistry storage sodium combination electrode, concrete preparation process is as follows:
By 2.5mmol graphene oxide ultrasonic disperse in 60mL deionized water, add 1.6mmol Dodecyl trimethyl ammonium chloride cationic surfactant, and be sufficiently stirred for, then it is sequentially added into 0.76g (6.25mmol) Cys and 0.3g (1.25mmol) sodium molybdate (Na2MoO4·2H2O), and be stirred continuously and make Cys and sodium molybdate be completely dissolved, volume extremely about 80mL is adjusted with deionized water, obtained mixed liquor is transferred in the hydrothermal reaction kettle of 100mL, this reactor is put in constant temperature oven, at 230 DEG C after hydro-thermal reaction 24h, it is allowed to naturally cool to room temperature, solid product is collected with centrifugation, and fully wash with deionized water, vacuum drying at 100 DEG C, by obtained solid product in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mixing gas, the volume fraction of hydrogen is 10%, prepares MoS2The nano composite material of nanometer sheet/Graphene, MoS in composite nano materials2It is 1:2 with the ratio of the amount of substance of Graphene.With XRD, SEM and TEM to finally preparing MoS2The nano composite material of nanometer sheet/Graphene characterizes, and XRD analysis result shows MoS in composite nano materials2For layer structure, its average number of plies is 7 layers, and TEM and HRTEM photo (see accompanying drawing 5) shows load MoS on Graphene2For nanometer sheet pattern, its thickness and plane sizes not as MoS above2Nanometer watt uniform, MoS2The number of plies of nanometer sheet is at 4-9 layer, and the average number of plies is 7 layers, consistent with XRD analysis.
It is electrochemistry storage sodium active substance by prepared MoS2 nanometer sheet/graphene composite nano material, by above-mentioned steps 3) process prepare MoS2 nanometer sheet/Graphene electrochemistry storage sodium combination electrode, and test its electrochemistry storage sodium performance by electrochemistry storage sodium method of testing same as before.Result shows: MoS2Nanometer sheet/Graphene electrochemistry storage sodium combination electrode electrochemistry storage initial reversible capacity of sodium is 253mAh/g(charging and discharging currents is 50mA/g), after 50 circulations, reversible capacity is 235mAh/g；When high current charge-discharge (charging and discharging currents is 1000mA/g), its capacity is 136mAh/g.
Claims (2)
1. the electrochemistry storage sodium combination electrode of a high power capacity and stable circulation, it is characterised in that the electrochemistry storage sodium active substance of combination electrode is MoS2Nanometer watt/composite nano materials of Graphene, MoS in composite nano materials2Nanometer watt and the ratio of amount of substance of Graphene be 1:1-1:3, MoS2Nanometer watt for the layer structure of few number of plies, the component of combination electrode and mass percentage content thereof be: MoS2Nanometer watt/graphene composite nano material 80%, acetylene black 10%, carboxymethyl cellulose 5%, Kynoar 5%, the preparation method of described combination electrode sequentially includes the following steps:
(1) by graphene oxide ultrasonic disperse in deionized water, add the double; two ammonium bromide of Gemini surface active agent N-dodecyl trimethylene diamine, and be sufficiently stirred for, then Cys and sodium molybdate it are sequentially added into, and be stirred continuously and make Cys and sodium molybdate be completely dissolved, the ratio of the amount of substance of Cys and sodium molybdate consumption is 5:1, and the ratio of sodium molybdate and the amount of substance of graphene oxide is 1:1-1:3；
(2) mixed dispersion that step (1) obtains is transferred in hydrothermal reaction kettle, and add deionized water and adjust volume to the 80% of hydrothermal reaction kettle nominal volume, the concentration of the double, two ammonium bromide of Gemini surface active agent N-dodecyl trimethylene diamine is 0.01～0.02mol/L, the content of graphene oxide is 30-65mmol/L, this reactor is put in constant temperature oven, at 230-250 DEG C after hydro-thermal reaction 24h, it is allowed to naturally cool to room temperature, hydro-thermal reaction solid product is collected with centrifugation, and fully wash with deionized water, vacuum drying at 100 DEG C, by the hydro-thermal reaction solid product that obtains in nitrogen/hydrogen mixed gas atmosphere at 800 DEG C heat treatment 2h, in mixing gas, hydrogen volume mark is 10%, finally prepare MoS2Nanometer watt/composite nano materials of Graphene；
(3) by the MoS of above-mentioned preparation2Nanometer watt/graphene composite nano material as prepare combination electrode electrochemistry store sodium active substance, the uniform pastel of furnishing under agitation it is sufficiently mixed with the N-Methyl pyrrolidone solution of the Kynoar of acetylene black, carboxymethyl cellulose and mass fraction 5%, this pastel is coated onto equably on the Copper Foil of collector, vacuum drying at 110 DEG C, rolling obtains MoS2Nanometer watt/Graphene electrochemistry storage sodium combination electrode.
2. the electrochemistry storage sodium combination electrode of high power capacity according to claim 1 and stable circulation, it is characterised in that described MoS2Nanometer watt the average number of plies be 4 layers.
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| CN110350159A (en) * | 2019-06-14 | 2019-10-18 | 天能电池集团股份有限公司 | A kind of combination electrode and preparation method thereof of simultaneous electrochemical storage lithium and storage sodium |
| CN110247038A (en) * | 2019-06-14 | 2019-09-17 | 天能电池集团股份有限公司 | A kind of Bi2S3-MoS2/ graphene composite nano material and preparation method thereof |
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